CN114345364A - Self-cleaning photo-thermal conversion multi-efficiency composite film material and preparation method and application thereof - Google Patents
Self-cleaning photo-thermal conversion multi-efficiency composite film material and preparation method and application thereof Download PDFInfo
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- CN114345364A CN114345364A CN202111587359.XA CN202111587359A CN114345364A CN 114345364 A CN114345364 A CN 114345364A CN 202111587359 A CN202111587359 A CN 202111587359A CN 114345364 A CN114345364 A CN 114345364A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
Hair brushThe composite photocatalytic film material is Cu2O film and WO3The film is formed by compounding a plurality of layers and has a structural general formula of [ Cu2O/WO3‑x]nWherein x represents an oxygen vacancy and 0. ltoreq. x<1, n represents the number of layers of the composite coating film, and n is a positive integer of 1-7. In the case of preparation, Cu2O film and WO3The multilayer compounding of the film can be realized by direct current magnetron sputtering coating. The composite photocatalytic film material disclosed by the invention is applied to solar photothermal conversion and utilization, film self-cleaning, photocatalytic degradation wastewater treatment and organic dust treatment. The invention utilizes binary Cu2O quantum dot character and binary WO3The energy band structure of the nano material is characterized in that the doping of two types of materials in a nano scale is implemented to construct a nano composite multilayer photocatalytic functional film, and the nano composite multilayer photocatalytic functional film is a multi-effect film material combining three performances of photo-thermal, self-cleaning and photocatalysis, and has lower reflectivity, better photo-induced hydrophilicity and excellent photocatalytic performance.
Description
Technical Field
The invention relates to a composite photocatalytic film material with multiple effects, a preparation method thereof, and application thereof in solar photothermal conversion utilization, film self-cleaning and photocatalytic degradation of printing and dyeing wastewater and organic dust treatment, and relates to the technical fields of photothermal, photocatalysis and self-cleaning.
Background
Along with the development of society, people have more and more demand on energy, the increasing mining strength of fossil fuels leads to the increasing serious energy crisis and environmental pollution, and the total energy consumption in 2019 is 5.88x10 according to statistics20J, fossil energy consumption of 4.99X 1030J, a share ratio of up to 84.8%, which also results in annual emissions of up to 371 hundred million tons of carbon dioxide worldwide; thus, it is important to enhance the clean and sustainable energy utilization. Statistically, the annual earth receives about 5x1024The energy of J solar radiation is 10000 times of the total energy consumed by human beings every year.Therefore, solar energy is one of the most likely replacements for traditional fossil energy, and is a clean energy source.
The solar photovoltaic cell has become one of the main means for utilizing solar energy, and the annual energy production of the solar photovoltaic cell is 1.2x1018J, only accounts for 37.5% of renewable energy, and still has great promotion space. However, the conversion efficiency of current commercial solar cells is only around 20%, which is due to the material itself on the one hand and is also related to the reflection of sunlight at the surface of the glass cover plate on the other hand. In order to improve the efficiency of the solar cell, people develop new materials on one hand, and on the other hand, the reflection of the glass cover plate to sunlight is weakened by plating one or more layers of antireflection films on the surface of the glass cover plate, so that the utilization rate of the glass cover plate to the sunlight is increased.
Generally speaking, for outdoor applications, the coating only has good antireflection performance, and cannot meet the requirements of the applications. This is because, with the passage of time, the surface of the film tends to adsorb some contaminants such as dust, which will seriously affect the antireflection effect; in addition, periodic cleaning of these contaminants will increase routine maintenance costs. Therefore, the cleaning mode which is as simple as possible, the cost of manual cleaning which is as low as possible and the power generation efficiency which is improved become the pursuit target of the photovoltaic power generation system, and the preparation of the antireflection film with the self-cleaning function is very important.
Generally, self-cleaning surfaces are divided into hydrophobic surfaces and hydrophilic surfaces. These superhydrophobic or superhydrophilic surface effects can be achieved by altering the surface structure or chemical composition. On hydrophobic surfaces, water droplets can quickly roll off the surface to remove contaminants due to the water repellency and low adhesion of the surface. However, the stability of organic superhydrophobic coatings under high intensity uv irradiation is to be improved. On hydrophilic surfaces, if a water droplet rapidly diffuses to the entire surface and forms a film of water, contaminants on the surface are washed away during the diffusion process.
The photocatalytic oxidation technology is an environment-friendly green technology, can thoroughly degrade organic pollutants, and the catalyst is nontoxic and cannot generateThe method can generate toxic byproducts, can react at normal temperature and normal pressure, thoroughly destroys the molecular structure of the organic matters, is used for degrading the organic matters deposited on the surface film material of the solar cell panel, and has the characteristics of high treatment efficiency, mild reaction, wide action range and the like. The mechanism process of the photocatalytic oxidation reaction is that under the irradiation of a specific light source, the photocatalyst generates photon-generated carriers to enable surrounding water molecules and oxygen to form extremely active free radicals (such as. OH free radicals and. O)2 -Free radical), can oxidize and degrade macromolecular organic matters into H2O and CO2And the like. The photocatalytic semiconductor material widely used at present is mainly TiO2、ZnO、CdS、WO3、SnO2And the like.
Disclosure of Invention
Aiming at the prior art and the problems of the existing photothermal film, the invention provides a composite film material which has multiple effects and combines three performances of photothermal, self-cleaning and photocatalytic degradation, a preparation method thereof and application thereof in solar photothermal conversion utilization, self-cleaning, organic dust degradation and printing and dyeing wastewater treatment.
The invention is realized by the following technical scheme:
a composite photocatalytic film material is prepared from Cu2O film (cuprous oxide film) and WO3The film (tungsten oxide film) is formed by multi-layer compounding and has a structural general formula of [ Cu2O/WO3-x]nWherein x represents an oxygen vacancy and 0. ltoreq. x<1, n represents the number of layers of the composite coating film, and n is a positive integer of 1-7.
Further, each layer of Cu2The thickness of the O film is 30 nm-105 nm, and each layer of WO3The thickness of the film is 30 nm-105 nm.
Further, the total thickness of the composite photocatalytic film material is 420 nm.
Further, the value of x is 0.2.
Further, the Cu2O film and WO3The multilayer compounding of the film is realized by direct current magnetron sputtering coating.
The preparation method of the composite photocatalytic film material comprises the following steps:
(1) preparation of thin film tungsten oxide
a. Mounting a target material of the coating chamber as a tungsten target, and vacuumizing; cleaning and drying the glass substrate, placing the glass substrate on a mask plate, fixing and sending the glass substrate into a sample chamber; the sample chamber is vacuumized, and when the vacuum degree of the sample chamber reaches 1 multiplied by 10-3When Pa is needed, opening a baffle between the sample chamber and the coating chamber, conveying the glass substrate into the coating chamber, and closing the baffle between the coating chamber and the sample chamber; vacuumizing the coating chamber, firstly vacuumizing by using a mechanical pump, then vacuumizing the coating chamber by using a molecular pump, and introducing argon (Ar); glow discharge, when the discharge color is stable and presents a blue-white color, preparing to start coating;
b. adjusting the sputtering power to 50W, adjusting the rotation speed of the turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, and introducing gas into the coating chamber to make the gas flow meter oxygen (O)2) The flow ratio of argon (Ar) to argon (Ar) was 1:3, and the total working pressure of the gas in the coating chamber was controlled to be 1X 10-5Pa, making the substrate in the range of glow discharge, starting timing film coating, and performing film coating for 1h in the atmosphere of stable glow discharge; after the direct-current magnetron sputtering is finished, transferring the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, and taking out the substrate coated with the film;
(2) preparation of thin film copper metal
Replacing the target material of the coating chamber in the step (1) a with a copper target, and repeating the operation in the step (1) a;
adjusting the sputtering power to 50W, adjusting the rotation speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, introducing gas into the film coating chamber to make the gas be in a quantitative mode, taking 45mL/min argon (Ar) as working gas, and simultaneously controlling the total working pressure of the gas in the film coating chamber to be maintained at 1 x10-5Pa, making the substrate in the glow discharge range, starting timing film coating, and performing film coating for 5s in the atmosphere of stable glow discharge;
(3) repeating the steps (1) and (2) until the requirement of the total thickness of the plated film is met;
after the direct-current magnetron sputtering is finished, transferring the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, and taking out the substrate coated with the film;
(4) annealing
And (3) placing the prepared copper-loaded tungsten oxide film in a tubular furnace, annealing in air at the annealing temperature of 500 ℃ and the heating rate of 5 ℃/min, and preserving heat for 1 h.
The composite photocatalytic film material is applied to the preparation of materials with the solar photo-thermal conversion utilization effect.
The composite photocatalytic film material is applied to being used as/preparing a material with a self-cleaning effect.
The composite photocatalytic film material is applied to the preparation of materials with the functions of photocatalytic wastewater degradation.
The composite photocatalytic film material is applied to the preparation of materials with the functions of photocatalytic degradation of organic dust.
Composite Cu and WO prepared by the above method3Film, annealed to Cu2O composite WO3Films with photothermal, self-cleaning, photocatalytic properties can be made by including Cu2O and WO3The component content, the thickness ratio of the film layer, the annealing temperature and other structural parameters are regulated and controlled.
The invention utilizes binary Cu2O quantum dot character and binary WO3The energy band structure of the nano material is used for implementing the doping of the two types of materials in the nano scale to construct the nano composite multilayer photocatalytic functional film. Compared with the traditional single-component photocatalytic material, the composite doped nano photocatalytic film has higher photocatalytic efficiency and longer service life.
Metallic oxide Cu2O is intrinsic of p type, WO3The semiconductor is an n-type semiconductor, and the two can form a p-n junction in combination, so that the generation of photon-generated carriers is facilitated. WO3At low conduction band levels, insufficient to provide O2The potential required for the reduction of a single electron, which inhibits reaction with an electron acceptor(ii) the ability to respond; and Cu2O has a sufficiently low conduction band to reduce oxygen, and Cu2O itself has strong adsorbability to oxygen, so Cu2O can be reduced under the excitation of light2Generating oxidising O2 -And the oxidative degradation of organic pollutants is realized.
Therefore, the composite photocatalytic film material disclosed by the invention is a multi-effect film material combining three performances of photo-thermal, self-cleaning and photocatalysis, and has the advantages of lower reflectivity, better photo-induced hydrophilicity and excellent photocatalysis performance.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD pattern) of a single tungsten oxide film, a copper-supported tungsten oxide film, and a cuprous oxide composite tungsten oxide film.
FIG. 2 is an Atomic Force Microscope (AFM) view of a single tungsten oxide film, a copper-supported tungsten oxide film, and a cuprous oxide composite tungsten oxide film, in which (a) the single tungsten oxide film is a plan view; (b) plan view of copper-supported tungsten oxide film; (c) a plan view of the cuprous oxide composite tungsten oxide film; (d) 3D drawing of a single tungsten oxide film; (e) 3D drawing of the copper-loaded tungsten oxide film; (f) and (3) 3D (three-dimensional) drawing of the cuprous oxide composite tungsten oxide film.
Fig. 3 is a line graph showing the transmittance of a single tungsten oxide film, a copper-supported tungsten oxide film, and a cuprous oxide composite tungsten oxide film.
Fig. 4 is a line graph of the reflectivity of three materials.
Fig. 5 is a schematic diagram showing a comparison of contact angles of a single tungsten oxide film, a copper-supported tungsten oxide film, and a cuprous oxide composite tungsten oxide film.
Fig. 6 is a graph showing the comparison of the methylene blue degradation rates of a single tungsten oxide film, a copper-supported tungsten oxide film, and a cuprous oxide composite tungsten oxide film.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
EXAMPLE 1 preparation of a multifunctional film of composite Nano-cuprous oxide and tungsten oxide (in this example, the total thickness of the composite is 420nm, the total number of layers is 7, the thickness of each layer of cuprous oxide and tungsten oxide is 30nm, and the value of x is 0.2)
The method comprises the following steps:
cleaning the surface and the back of a glass substrate to remove dust particles, organic and inorganic impurities, which comprises the following steps:
(a) placing the glass substrate in deionized water, ultrasonically cleaning for 5 minutes, and cleaning surface dust;
(b) placing the glass substrate in an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the glass substrate;
(c) placing the glass substrate in an ethanol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the glass substrate;
(d) and taking out the glass substrate, and drying the surface solution for later use.
(II) preparing Cu by adopting magnetron sputtering method2O/WO3-xThe composite multilayer nano film comprises the following specific components:
(a) changing targets and vacuumizing a coating chamber: and closing the vacuum of the coating chamber, and installing the target material as a tungsten target. Starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the order of magnitude of vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, and utilizing the molecular pump to control the magnetic control chamberHigh vacuum is pumped, and an ionization vacuum gauge is observed at the same time, when the vacuum degree reaches 10 multiplied by 10-5And (6) closing a molecular pump valve of the film coating chamber while Pa is kept. And simultaneously opening an argon (Ar) gas tank valve, adjusting a molecular pump valve, observing a vacuum gauge, and fixing the position of the molecular pump valve when the working pressure of the coating chamber reaches 1.0 Pa.
(b) Fixing the glass substrate: and (3) placing the cleaned glass substrate on a tray, fixing, opening an air release valve of the sample chamber, opening a window of the sample chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, placing a mask plate in the sample chamber, and closing the valve of the sample chamber.
(c) Vacuumizing a sample: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the sample chamber is turned on, a vacuum gauge of the sample chamber is observed, when the magnitude of vacuum degree of the sample chamber reaches the vacuum degree of the coating chamber, a baffle between the sample chamber and the coating chamber is opened, a tray rotating shaft in the sample chamber is rotated, the substrate is conveyed into the coating chamber, a mechanical arm of the coating chamber is used for placing the substrate on a rotating disk of the substrate, a standby mechanical arm returns to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(d) Glow discharge: and (3) turning on a 500W direct current working source, adjusting the power of a direct current regulator to 50W, finding glow discharge in the magnetron chamber, pre-sputtering for 5min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
(e) Preparation of WO by direct current magnetron sputtering3-xNano film: adjusting the sputtering power to 50W, adjusting the rotation speed of the turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, opening the valve of the oxygen tank and introducing oxygen (O) into the film coating chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:3, while adjusting the valves of the molecular pump so that the total operating pressure of the gas in the magnetron chamber is maintained at 10-5Pa, making the substrate in the range of glow discharge, starting timing film coating, and performing film coating for 1h in the atmosphere of stable glow discharge; after the direct current magnetron sputtering is finished, the substrate is putThe film coating chamber is conveyed back to the sample chamber, the vacuum of the sample chamber is closed, the pressure intensity of the sample chamber is adjusted, and the substrate coated with the film is taken out.
(f) Preparing a Cu nano film by direct current magnetron sputtering: and (4) replacing the target material of the coating chamber with a copper target, and repeating the rest steps. Adjusting the sputtering power to 50W, adjusting the rotating speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, opening a valve of an argon tank to introduce argon (Ar) into the coating chamber, adjusting a gas flowmeter to ensure that the flow of the argon (Ar) of the gas flowmeter is 45mL/min, adjusting a valve of a molecular pump to ensure that the total working pressure of the gas in the magnetron chamber is kept at 10-5Pa, ensuring that the substrate is in the range of glow discharge, starting timing coating, and coating for 5s in the atmosphere of stable glow discharge.
Thirdly, repeating the steps (1) and (2) until the total thickness of the plated film is 420 nm;
(IV) taking out the substrate with the plated film: and after the direct-current magnetron sputtering is finished, adjusting the power of the direct-current matcher to be zero, and simultaneously closing the 500W direct-current working source. The valve of the argon tank is closed and the gas flow meter is adjusted to zero. Closing the valve of the molecular pump, setting the rotation speed of the molecular pump to zero, opening the valve of the mechanical pump, opening the baffle between the sample chamber and the coating chamber when the vacuum degrees of the sample chamber and the coating chamber are in one order of magnitude, then sending the tray of the sample chamber into the magnetic control chamber, taking down the tray by using a mechanical arm, and sending the tray back to the sample chamber. And closing a baffle between the sample chamber and the coating chamber, and closing a mechanical pump valve of the coating chamber and a power supply of a mechanical pump vacuum gauge. And opening a sample chamber gas release valve, opening a window of the sample chamber when the pressure in the sample chamber is equal to the external atmospheric pressure, taking out the tray, unloading the substrate coated with the film from the tray, and storing the substrate in a sample box.
(V) annealing
WO is loaded on the prepared Cu3-xAnd (3) placing the film in a tube furnace, opening an air valve, opening a heating device, annealing the sample in the air, regulating and controlling the annealing temperature to be 500 ℃, controlling the heating rate to be 5 ℃/min, and preserving the heat for 1 h. When the temperature of the annealing furnace is reduced to the room temperature, the temperature control device is closed, and the sample is taken out of the quartz tubeAnd taking out the sample, and putting the sample into a sample box for storage so as to be used in subsequent application experiments.
Comparative example 1 preparation of a Single tungsten oxide film (Total thickness 420nm, x 0.2)
The method comprises the following steps:
cleaning the surface and the back of a glass substrate to remove dust particles, organic and inorganic impurities, which comprises the following steps:
(a) putting the substrate into deionized water, and ultrasonically cleaning for 5 minutes to clean dust on the surface;
(b) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(c) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(d) taking out the substrate, and drying the surface solution for later use.
(II) preparing WO by adopting magnetron sputtering method3-xPreparation of monolayer nano-film:
(a) changing targets and vacuumizing a coating chamber: and closing the vacuum of the coating chamber, and installing the target material as a tungsten target. Starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the order of magnitude of vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, utilizing the molecular pump to pump high vacuum to the magnetic control chamber, observing an ionization vacuum gauge simultaneously, and observing the ionization vacuum gauge when the vacuum degree reaches 10 multiplied by 10-5And (6) closing a molecular pump valve of the film coating chamber while Pa is kept. And simultaneously opening an argon (Ar) gas tank valve, adjusting a molecular pump valve, observing a vacuum gauge, and fixing the position of the molecular pump valve when the working pressure of the coating chamber reaches 1.0 Pa.
(b) Fixing the glass substrate: and (3) placing the cleaned glass substrate on a tray, fixing, opening an air release valve of the sample chamber, opening a window of the sample chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, placing a mask plate in the sample chamber, and closing the valve of the sample chamber.
(c) Vacuumizing a sample: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the sample chamber is turned on, a vacuum gauge of the sample chamber is observed, when the magnitude of vacuum degree of the sample chamber reaches the vacuum degree of the coating chamber, a baffle between the sample chamber and the coating chamber is opened, a tray rotating shaft in the sample chamber is rotated, the substrate is conveyed into the coating chamber, a mechanical arm of the coating chamber is used for placing the substrate on a rotating disk of the substrate, a standby mechanical arm returns to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(d) Glow discharge: and (3) turning on a 500W direct current working source, adjusting the power of a direct current regulator to 50W, finding glow discharge in the magnetron chamber, pre-sputtering for 5min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
(III) preparation of WO by direct-current magnetron sputtering3-xNano film: adjusting the sputtering power to 50W, adjusting the rotation speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, opening a valve of an oxygen tank to introduce oxygen (O2) into the coating chamber, adjusting a gas flow meter to ensure that the flow ratio of the oxygen (O2) and argon (Ar) of the gas flow meter is 1:3, and adjusting a valve of a molecular pump to ensure that the total working pressure of the gas in the magnetron chamber is kept at 10-5Pa, making the substrate in the glow discharge range, starting timing film coating, and performing film coating for 1h in the atmosphere of stable glow discharge.
Repeating the steps to carry out film coating until the thickness of the film coating is 420 nm;
(IV) taking out the substrate with the plated film: and after the direct-current magnetron sputtering is finished, adjusting the power of the direct-current matcher to be zero, and simultaneously closing the 500W direct-current working source. The valve of the argon tank is closed and the gas flow meter is adjusted to zero. Closing the valve of the molecular pump, setting the rotation speed of the molecular pump to zero, opening the valve of the mechanical pump, opening the baffle between the sample chamber and the coating chamber when the vacuum degrees of the sample chamber and the coating chamber are in one order of magnitude, then sending the tray of the sample chamber into the magnetic control chamber, taking down the tray by using a mechanical arm, and sending the tray back to the sample chamber. And closing a baffle between the sample chamber and the coating chamber, and closing a mechanical pump valve of the coating chamber and a power supply of a mechanical pump vacuum gauge. And opening a sample chamber gas release valve, opening a window of the sample chamber when the pressure in the sample chamber is equal to the external atmospheric pressure, taking out the tray, unloading the substrate coated with the film from the tray, and storing the substrate in a sample box.
(V) annealing
WO to be prepared3-xAnd (3) placing the film in a tube furnace, opening an air valve, opening a heating device, annealing the sample in the air, regulating and controlling the annealing temperature to be 500 ℃, controlling the heating rate to be 5 ℃/min, and preserving the heat for 1 h. And when the temperature of the annealing furnace is reduced to the room temperature, closing the temperature control device, taking the sample out of the quartz tube, and putting the sample into a sample box for storage for subsequent application experiments.
Comparative example 2 composite nanocu and WO3-xThe preparation of the multifunctional thin film (total thickness is 420nm, total number of layers is 7, thickness of each layer of copper and tungsten oxide is 30nm, and value of x is 0.2)
The method comprises the following steps:
cleaning the surface and the back of a glass substrate to remove dust particles, organic and inorganic impurities, which comprises the following steps:
(a) putting the substrate into deionized water, and ultrasonically cleaning for 5 minutes to clean dust on the surface;
(b) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(c) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(d) taking out the substrate, and drying the surface solution for later use.
(II) preparing Cu/WO by adopting magnetron sputtering method3-xPreparation of composite multilayer nano-film:
(a) changing targets and vacuumizing a coating chamber: and closing the vacuum of the coating chamber, and installing the target material as a tungsten target. Starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the magnitude of the vacuum degree in the magnetic control chamber reaches the power of zero, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min,at the same time, the gate valve of the molecular pump is opened, the mechanical pump drives the molecular pump to operate, the molecular pump is used for pumping high vacuum to the magnetic control chamber, and the ionization vacuum gauge is observed, when the vacuum degree reaches 10 multiplied by 10-5And (6) closing a molecular pump valve of the film coating chamber while Pa is kept. And simultaneously opening an argon (Ar) gas tank valve, adjusting a molecular pump valve, observing a vacuum gauge, and fixing the position of the molecular pump valve when the working pressure of the coating chamber reaches 1.0 Pa.
(b) Fixing the glass substrate: and (3) placing the cleaned glass substrate on a tray, fixing, opening an air release valve of the sample chamber, opening a window of the sample chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, placing a mask plate in the sample chamber, and closing the valve of the sample chamber.
(c) Vacuumizing a sample: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the sample chamber is turned on, a vacuum gauge of the sample chamber is observed, when the magnitude of vacuum degree of the sample chamber reaches the vacuum degree of the coating chamber, a baffle between the sample chamber and the coating chamber is opened, a tray rotating shaft in the sample chamber is rotated, the substrate is conveyed into the coating chamber, a mechanical arm of the coating chamber is used for placing the substrate on a rotating disk of the substrate, a standby mechanical arm returns to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(d) Glow discharge: and (3) turning on a 500W direct current working source, adjusting the power of a direct current regulator to 50W, finding glow discharge in the magnetron chamber, pre-sputtering for 5min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
(III) preparation of WO by direct-current magnetron sputtering3-xNano film: adjusting the sputtering power to 50W, adjusting the rotation speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, opening a valve of an oxygen tank to introduce oxygen (O2) into the coating chamber, adjusting a gas flow meter to ensure that the flow ratio of the oxygen (O2) and argon (Ar) of the gas flow meter is 1:3, and adjusting a valve of a molecular pump to ensure that the total working pressure of the gas in the magnetron chamber is kept at 10-5Pa, making the substrate in the glow discharge range, starting timing coating, and stabilizing glowCoating for 1h in the atmosphere of light discharge;
repeating the steps to carry out film coating until the thickness of the film coating is 420 nm;
and after the direct-current magnetron sputtering is finished, transferring the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, and taking out the substrate coated with the film.
(IV) annealing
WO to be prepared3-xAnd (3) placing the film in a tube furnace, opening an air valve, opening a heating device, annealing the sample in the air, regulating and controlling the annealing temperature to be 500 ℃, controlling the heating rate to be 5 ℃/min, and preserving the heat for 1 h. And when the temperature of the annealing furnace is reduced to the room temperature, closing the temperature control device, taking the sample out of the quartz tube, and putting the sample into a sample box for storage.
(V) preparing a Cu nano film by direct current magnetron sputtering: and (3) replacing the target material of the coating chamber in the step (2) with a copper target, and repeating the rest steps. Adjusting the sputtering power to 50W, adjusting the rotating speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, opening a valve of an argon tank to introduce argon (Ar) into the film coating chamber, adjusting a gas flowmeter to ensure that the flow of the argon (Ar) of the gas flowmeter is 45mL/min, and adjusting a valve of a molecular pump to ensure that the total working pressure of the gas in the magnetron chamber is kept at 10 DEG-5Pa, making the substrate in the glow discharge range, starting timing film plating, and performing film plating for 5s in the atmosphere of stable glow discharge. And after sputtering is finished, conveying the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, taking out the substrate coated with the film, and storing the substrate in a sample box for later application experiments.
Testing of experimentally related Properties
(1) The three film materials obtained above were subjected to structural and performance characterization, and the results are shown in fig. 1 and fig. 2. According to an atomic force microscope, the metal copper-loaded tungsten oxide film is better in crystallinity, larger in particle size and darker in picture, and the copper-loaded tungsten oxide film is higher in roughness by combining a 3D image. The cuprous oxide composite tungsten oxide has relatively flat film surface, higher density and better fusion property because the metal copper and the tungsten oxide are annealed together. The average roughness (SA) of the copper-supported tungsten oxide film and the cuprous oxide composite tungsten oxide film was 6.119 and 7.996, respectively, which were about 1.5 times that of the single tungsten oxide film (4.776). The differences in crystallinity and roughness, as well as the p-n junction formed by cuprous oxide and tungsten oxide, can differentiate the material's ability to degrade contaminants.
(2) As can be seen from FIGS. 3 and 4, the transmittance of the three thin film materials shows a peak-to-valley value, the transmittance of the sample in the wavelength range of less than 380nm is small mainly due to intrinsic absorption of the materials, and the fluctuation of the transmittance in the wavelength range of more than 400nm is an interference phenomenon with the substrate surface determined by the refractive index of the thin film and the film thickness. Among them, the copper-supported tungsten oxide film has a lower transmittance than cuprous oxide because the former film has a high surface roughness, so that its light scattering loss is large and the transmittance is low. The reflectance is distinguished primarily in that an increase in crystallinity increases density, resulting in a decrease in reflectance.
(3) Fig. 5 is a contact angle comparison graph of photo-induced hydrophilicity, three film materials are respectively taken out after being irradiated for 30 minutes under a photocatalysis reactor, and contact angles of the three film materials are immediately tested to obtain a photo-induced hydrophilicity contact angle value.
As can be seen from fig. 5, the thin film material of cuprous oxide-supported tungsten oxide has the smallest contact angle, i.e., the best hydrophilicity, while the thin film material of copper-supported tungsten oxide has the worst hydrophilicity, with a single thin film material of tungsten oxide having hydrophilicity in the middle. The surface contact angle of the film is determined by the surface tension of three interfaces of solid phase-gas phase, liquid phase-solid phase and liquid phase-solid phase, and the good hydrophilicity of the cuprous oxide loaded tungsten oxide film material is probably due to the fact that the surface energy of the film is reduced by doping.
(4) Organic dust and methylene blue simulated wastewater degradation tests were performed on the cuprous oxide composite tungsten oxide film obtained in example 1, the single oxide film obtained in comparative examples 1 and 2, and the copper-supported tungsten oxide film, respectively, and the results are shown in table 1 and fig. 6.
TABLE 1 comparison of the organic dust degradation rates of the three materials
A verification experiment that the cuprous oxide composite tungsten oxide and the single tungsten oxide film and the copper-loaded tungsten oxide film obtained in the comparative examples 1 and 2 are used for treating organic dust (oil sludge is used as a main component) with the thickness of 3mm in a self-made photocatalytic reaction device is continuously carried out for 12, 24 and 36 hours, a weight loss method is adopted for measurement, and the formula of the degradation rate is as follows: degradation rate (%) — weight of sample before degradation-weight of sample after degradation/weight of sample before degradation. Experiments show that the degradation rate of the cuprous oxide composite tungsten oxide film reaches 94% in 36 hours, while the removal rate of a single tungsten oxide film is only 42%, and specific results are shown in table 1.
The photocatalytic activity test is carried out in a home-made photocatalytic reaction device. Using a 10mg/L methylene blue solution (MB, C)16H19C1N3S·3H2O) to determine the photocatalytic activity of the three thin film materials. And (3) putting the film material into a glass beaker, immersing the film in 10mg/L methylene blue solution for half an hour under a dark condition, and allowing the surface adsorption of the film material to reach balance. A xenon lamp is used as a light source, a sample is vertically irradiated at a position which is about 15cm away from the sample, the absorbance of the MB solution after different irradiation time is measured by an ultraviolet-visible spectrophotometer under 664nm, the absorbance of the MB is converted into concentration by using Lambert-Beer law, and then the photocatalytic efficiency of the film is analyzed. FIG. 6 is a degradation curve of methylene blue, and it can be seen from the graph that when the photocatalytic experiment is performed for 45 minutes, the removal rate of the cuprous oxide composite tungsten oxide film reaches 68%, while the removal rate of a single tungsten oxide film is the lowest, and is 61%; this is because the metal oxide Cu2The O intrinsic is p-type, the tungsten oxide is n-type semiconductor, and the two form a p-n junction, which is beneficial to forming a photon-generated carrier; and Cu2O itself has strong adsorbability to oxygen, so Cu2O can be reduced under the excitation of light2Generating oxidising O2 -And the oxidative degradation of organic pollutants is realized.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. A composite photocatalytic film material is characterized in that: is made of Cu2O film and WO3The film is formed by compounding a plurality of layers and has a structural general formula of [ Cu2O/WO3-x]nWherein x represents an oxygen vacancy and 0. ltoreq. x<1; n represents the number of layers of the composite coating film, and n is a positive integer of 1-7.
2. The composite photocatalytic film material according to claim 1, wherein: each layer of Cu2The thickness of the O film is 30 nm-105 nm, and each layer of WO3The thickness of the film is 30 nm-105 nm.
3. The composite photocatalytic film material according to claim 1, wherein: the total thickness of the composite photocatalytic film material is 420 nm.
4. The composite photocatalytic film material according to claim 1, wherein: the value of x is 0.2.
5. The composite photocatalytic film material according to claim 1, wherein: the Cu2O film and WO3The multilayer compounding of the film is realized by direct current magnetron sputtering coating.
6. The preparation method of the composite photocatalytic film material as set forth in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
(1) preparation of thin film tungsten oxide
a. Mounting a target material of the coating chamber as a tungsten target, and vacuumizing; cleaning and drying the glass substrate, placing the glass substrate on a mask plate, fixing and sending the glass substrate into a sample chamber; the sample chamber is vacuumized, and when the vacuum degree of the sample chamber reaches 1 multiplied by 10-3At Pa timeOpening a baffle between the sample chamber and the coating chamber, conveying the glass substrate into the coating chamber, and closing the baffle between the coating chamber and the sample chamber; vacuumizing the coating chamber, firstly vacuumizing by using a mechanical pump, then vacuumizing the coating chamber by using a molecular pump, and introducing argon; glow discharge, when the discharge color is stable and presents a blue-white color, preparing to start coating;
b. adjusting the sputtering power to 50W, adjusting the rotation speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, introducing gas into the film coating chamber to make the flow ratio of oxygen to argon of the gas flowmeter be 1:3, and simultaneously controlling the total working pressure of the gas in the film coating chamber to be maintained at 1 x10-5Pa, making the substrate in the range of glow discharge, starting timing film coating, and performing film coating for 1h in the atmosphere of stable glow discharge; after the direct-current magnetron sputtering is finished, transferring the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, and taking out the substrate coated with the film;
(2) preparation of thin film copper metal
Replacing the target material of the coating chamber in the step (1) a with a copper target, and repeating the operation in the step (1) a;
adjusting the sputtering power to 50W, adjusting the rotation speed of a turntable of the glass substrate to 5rpm, setting the temperature of the glass substrate to room temperature, introducing gas into the film coating chamber to make the gas be in a quantitative mode, taking 45mL/min argon as working gas, and simultaneously controlling the total working pressure of the gas in the film coating chamber to be maintained at 1 x10-5Pa, making the substrate in the glow discharge range, starting timing film coating, and performing film coating for 5s in the atmosphere of stable glow discharge;
(3) repeating the steps (1) and (2) until the requirement of the total thickness of the plated film is met;
after the direct-current magnetron sputtering is finished, transferring the substrate from the coating chamber back to the sample chamber, closing the vacuum of the sample chamber, adjusting the pressure of the sample chamber, and taking out the substrate coated with the film;
(4) and (6) annealing.
7. The application of the composite photocatalytic film material as described in any one of claims 1 to 5 in the preparation of materials with solar photo-thermal conversion utilization effects.
8. The use of the composite photocatalytic film material as defined in any one of claims 1-5 as a material with self-cleaning effect.
9. The use of the composite photocatalytic film material as defined in any one of claims 1 to 5 as a material for photocatalytic degradation of wastewater.
10. The use of the composite photocatalytic film material as defined in any one of claims 1 to 5 as a material for photocatalytic degradation of organic dust.
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